Dyeing and printing of polymers of acyrlonitrile



United-ism Q DYEING AND Pizmrme, or POLYMERS F ACYRLONITRILE 3 Claims; (oi.

Patented Sept. 29,1959,

1131ivi ii ii ei lifil lt I 35 I ofipo lyrners. of acrylonitrile; more particularly it'r-- e arretssa ra' i n g nd pa n e prising acrylonitrile polymerswit-h oxa'ziiie' dyest'iifis, of the general formula alli'yl oi shbstit uteif antyrg- R, stands for alkyl, substituted alkyl, aryl or aralkyl, lhmeanshydrogen or. a CH CH -CH or t H;- gibu'fi liiiker'i to the 'aroiriatic nucleus in o -positibn to 'iid x-s'ta'rids fo'r aii acid-radical; v comprising acrylonitrile'polynieis tliere may fie rfreii'tioiie d fibres; filaments, fabrics, nioulded articles and die like." A'lsbacrylonit'ril copolyrners containing at least 85% byweight; of acrylonitrile can be dyed according to the invention.

It is an object of this invention to provide a process for dyeing and printing: articl'es prepared from acrylonitrile polymerscontaiiiingi at least 85% by weight of acrylonitrile. A further object is the provision of dyed and printed acrylonitrile; polymers a'iid copolymers, the

S-hydroxynaphthalenes. p

Suitable components for the production of the dyestuffs? are 'for example- 4 nit'rbfsb -3-hydioxy-N diihetliyl; aiiilih'e, -4riitrosd 3 liyd'roiiy N diethylaniline, 4=nitrbso 3 hydroxy N ethyl N liydioxythyl aniliiie, 4 nitro'so'=3 drox mnietlryl N cliloroethyl anilineg 4 -nitroso na hy droxy=N rnethyl N-cyanethylaniline;- 4 --n'iti'osb-- dr6xy N,N dihydroxyetliyl aniline, 4"- nitro'so 3-hydr N,N-dichlbroethyl*-aniline; 4= nitroso '3 -liydroxyN, N'-di cyanemynannine; 4'"- nitio'so-B hydroxy- 2--'chlbro ;N"- methyla'riiliii} 4*-nitros'o' 3'- hydroxy 5-metliyl NiN di' methylaniline, 4 nitroso 3,6 dihydroxy-N,N-dimethylaniline, 4 nitroso 3. hydroxy 4' methyl-N-methyl-diphenylamine, 4-dimethylamino-2-hydroxy-azobenzene, 4-

dimethylamino-2 hydroxy azobenzene-4-sulfonic acid, 1-

amino-5-hydroxynaphthalene; 7 h'ydroxy-l,2,3,4-tetral1ydrobenzoquinolirie, py-S-hydroxyI-l,2,3,4-tetrahydro-7-hydroxybenzoquirroline.

For the formaiton: of salts' according; to the general definition the following acids are suitable for example:

I agehtfiofiexarriple' a'pblyglycol ether of aliigli'molecular dyeings and prints obtained being distinguished by good a fastness properties According to the invention it has been found that valuable dyeingsiand prints may be obtained on polymers orcopolymers acrylonitrile by using oxazine dyestuffs --NH-, and X stands for an acid radical. The aromatic radicals of: the oxazine. dyestufismay contain. further sub- ThQq dyestuig'stusedl accordinglto, the invention may lie weight fatty arcomn, 'er'soap. The instructionsgiven fbiri the dyeing apply in principle also to the printing of poli acrylonitrile fibres.

The dyeings obtainable in; this way have very good fastness properties. The excellent fastness to light should be especially noted. The dyeings obtainable ac cording to the process of the invention differ therein in an advantageous manner from the dyeings obtained by the process of: French patent specification 1,099,280.

The following examples are given. forv the purpose of illustrating the invention without, however, limiting it thereto.

Example 1 20 grams of the hydrochloride of 1-amino-5-hydroxy- I naphthalene and 31 grams of the hydrochloride of 4- produced by known methods, for examplej. tlier'e'action of 4-r1itroso-3-hydroxy-arriinoberi2eiies'with l-arfiiii'dgroup linked to the aromatic nucleus in o-positionto nitroso-3- hydroxy-l-dimethylarninobenzene in grams of. glacial aceti'c a'cid and 2O grams of water are remixed for 2 hours; The" contents of the flask arewhen poured into 300 grams of ice water, and the oxaziire dyestuif thus obtained is salted out with a 20 percent solution of common salt. It corresponds to the formula Example 2 8.6 grams of the hydrochloride of 1,2,3,4-tetrahydro- 3-hydroxy-(7,8,1,2') 6' hydroxy benzoquinoline in 50 grams of glacial acetic acid are heated to the boil with stirring. 10.8 grams of the hydrochloride of 4-nitroso-3- hydroxy-l-diethylamino-benzene in 50 grams of glacial acetic acid are then added to the solution and the mixture is boiled for 10 minutes. The mixture is then poured into 250 grams of ice water and the dyestulf salted out with common salt. It corresponds to the formula The dyestulf is dyed on polyacrylonitrile fibres according to the instruction given in Example 1 whereby bluish green shades are obtained which are very fast to light.

Example 3 12.5 grams of the hydrochloride of 1,2,3,4-tetrahydro- 3-hydroxy-(7,8,1,2) 6 hydroxybenzoquinoline and 16 grams of the hydrochloride of 4-nitroso-3-hydroxy-1- (N-ethyl-N-hydroxyethyl)-aniline in 50 grams of glacial acetic acid are refluxed for 10 minutes. The mixture is then poured into 250 grams of ice water and the dyestuff salted out with common salt. It corresponds to the formula:

The dyestuff is dyed on polyacrylonitrile fibres according to the instructions given in Example 1 whereby bluish green shades are obtained having very good fastness to light.

Example 4 24 grams of 3-hydroxy-(N-ethyl-N-chloroethyl)-aniline are dissolved in 125 grams of glacial acetic acid and treated at -5" C. with 8.5 grams of sodium nitrite in 20 grams of water. After reaction is completed thereto are added 18 grams of the hydrochloride of l-amino-S- hydroxy-naphthalene and the mixture is refluxed with stirring for 15 minutes. The contents of the flask are then poured into 500 grams of ice water and the dyeliquid-to-goods i 4 stuff is precipitated with the addition of sodium chloride solution. It corresponds to the formula and dyes polyacrylonitrile fibres with the addition of a dispersing agent in reddish blue shades.

Example 5 37 grams of the hydrochloride of 4-nitroso-3-hydroxy- (N-methyl-N-cyanethyl)-aniline and 16 grams of l-amino- S-hydroxy-naphthalene are refluxed in grams of glacial acetic acid for 30 minutes. The mixture is then poured into 300 grams of ice water and the dyestuff is isolated by adding sodium chloride solution. The dyestufi which corresponds to the following formula:

CQHCN dyes polyacrylonitrile fibres in reddish blue shades.

Example 6 20 grams of l,2,3,4-tetrahydro-7-hydroxy-benzoquinoline and 28 grams of the hydrochloride of 4-nitroso-3- hydroxy-l-dimethylaminobenzene are refluxed in 100 grams of glacial acetic acid and 20 grams of water for 1 hour. The contents of the flask are then poured into 300 grams of ice water and the oxazine dyestutf is precipitated with the addition of sodium chloride solution. The dyestuff thus obtained corresponds to the formula It dyes polyacrylonitrile fibres according to the method described in Example 1 in greenish blue shades having very good fastness properties.

Example 7 A fabric containing polyacrylonitrile is printed with a printing paste of the following composition:

30 grams of the oxazine dyestufi described in Example 1,

30 grams of acetic acid (30 percent),

500 grams of crystal gum (gum arabic used as thickener),

360 grams of water,

30 grams of zinc nitrate solution (d 1.5),

50 grams of thiocliethylene glycol.

1000 grams The print thus obtained is dried, steamed for 30 minutes and subsequently rinsed with water. A bluish green print is obtained having very goodfastness properties,

e pecially very good fastness to light.

We claim: 1. An oxazine dyestuff corresponding to the formula wherein R means a radical selected from the group consisting of hydrogen, alkyl and substituted alkyl, R; stands for a member selected from the group consisting of alkyl, substituted alkyl, aralkyl and aryl, R means a radical selected from the group consisting of hydrogen, and a --CH CH CH and --CH -(|3HOHz-- OH group linked to the aromatic nucleus in o-position to NH, and X stands for an acid radical selected from the group consisting of hydrohalic acid, sulfuric acid, phosphoric acid, amino sulfonic acid, formic acid, acetic acid, propionic acid, cloroacetic acid and oxalic acid.

2. Articles prepared from acrylonitrile polymers containing at least 85% by weight of acrylonitrile, said articles being dyed with oxazine dyestuifs corresponding to the formula wherein R means a radical selected from the group consisting of hydrogen, alkyl and substituted alkyl, R, stands for a member selected from the group consisting of alkyl, substituted alkyl, aralkyl and aryl, R means a radical selected from the group consisting of hydrogen, and a and CHg-CH-CH wherein R means a radical selected from the group consisting of hydrogen, alkyl and substituted alkyl, R stands for a member selected from the group consisting of alkyl, substituted alkyl, aralkyl and aryl, R means a radical selected from the group consisting of hydrogen, and a -CH CH -CH and CHr-CII-CHggroup linked to the aromatic nucleus in o-position to NH, and X stands for a radical of an acid selected from the group consisting of hydrohalic acid, sulfuric acid, phosphoric acid, aminosulfonic acid, formic acid, acetic acid, propionic acid, chloroacetic acid, and oxalic acid.

References Cited in the file of this patent FOREIGN PATENTS France Sept. 1, 1955 Great Britain June 27, 1956 OTHER REFERENCES Chem. and Eng. News for September 10, 1956, p. 4359 (art. by Schroeder).

The J. of the Soc. of Dyers and colouris s fo June 1956, p. 263 (art. by Walls), 

2.ARTICLES PREPARED FROM ACRYLNITRILE POLYMERS CONTAINING AT LEAST 85% BY WEIGHT OF ACRYLONITRILE, SAID ARTICLES BEING DYED WITH OXAZINE DYESTUFFS CORRESPONDING TO THE FORMULA 